CN104119482A - Mud-resistant polycarboxylic acid water-reducing agent and preparation method thereof - Google Patents
Mud-resistant polycarboxylic acid water-reducing agent and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a mud-resistant polycarboxylic acid water-reducing agent and a preparation method thereof. The mud-resistant polycarboxylic acid water-reducing agent disclosed by the invention is prepared by copolymerizing an unsaturated polyalkylene dialcohol ether monomer a, an unsaturated carboxylic acid monomer b, unsaturated acid hydroxyalkyl ester c and an ammonium salt cationic unsaturated monomer d through free radicals under the action of an initiator and a chain transfer agent; and the mol ratio of the monomer a to the monomer b to the monomer c to the monomer d is 1.0:(2.0-4.2):(0.2-1.0):(0.1-0.5). Under the condition that aggregates contain mud, the dispersion effect of the mud-resistant polycarboxylic acid water-reducing agent disclosed by the invention is obviously prior to that of the traditional water-reducing agent; and the mud-resistant polycarboxylic acid water-reducing agent not only has low amount of admixture but also has better keeping property.
Description
Technical field
The present invention relates to concrete admixture preparation field, more specifically to a kind of, can effectively resist anti-chamotte mould polycarboxylate water-reducer of earth disadvantageous effect and preparation method thereof.
Background technology
High performance concrete is generally comprised of cement, coarse-fine aggregate, high-performance water reducing agent and water etc., wherein high-performance water reducing agent and the starting material that are all absolutely necessary that gather materials.Polycarboxylate water-reducer is because have the advantages such as volume is low, water-reducing rate is high, concrete contraction percentage is low, environmental protection, become a kind of important materials of manufacturing high performance concrete, in many engineerings such as water conservancy and hydropower, Highrise buildings, subway tunnel, be widely used.But find in concrete actual production process, tradition polycarboxylate water-reducer is very responsive to the silt content in aggregate, along with the increase of silt content, dispersing property and the function of slump protection of traditional polycarboxylate water-reducer obviously reduce, and the serviceability of fresh concrete declines to a great extent.Increase water reducer volume, though initial flow degree makes moderate progress, collapsing, damage is too fast still cannot be solved.
It is mainly because have the type clay expanding with water as polynite in earth that earth in aggregate makes the dispersing property of polycarboxylate water-reducer and function of slump protection reduction, this clay has 2:1 type structural sheet, its layered crystal structure makes clay have abundant pore passage structure and interlamellar spacing adjustability, can between clay crystal layer, there is intercalation in polycarboxylate water-reducer, thereby in a large number by adsorption by clay, cause the dispersion efficiency of polycarboxylate water-reducer to reduce.
Under, sandstone quality overall situation worse and worse day by day deficient in current quality sand and stone resources, develop inferior quality sandstone significant.Therefore the necessary way that finds solves the disadvantageous effect that dispersion effect that the earth in aggregate brings to polycarboxylate water-reducer significantly reduces.
For solving aggregate, contain the disadvantageous effect that mud brings, patent CN102358763B and patent application CN102093519A, CN102923989A are all synthetic water reducers with anti-mud effect, but the water reducer of the type still can be adsorbed by earth, not high, the actual anti-mud DeGrain of water-reducing rate; And patent application CN101798197 terms of settlement is to mix retardant and sustained release dosage in polycarboxylate water-reducer, its characteristic component is 75～95 parts of polycarboxylate water-reducers, 2～15 parts of retardant, 5～25 parts of sustained release dosages, wherein sustained release dosage is natural zeolite powder, retardant is Sunmorl N 60S or Trisodium Citrate or sucrose, though there is certain effect, but after adding natural zeolite powder, can cause water reducer state labile, zeolite powder is precipitation and water reducer layering easily.
Summary of the invention
Technical problem to be solved by this invention is can reduce the dispersion of traditional water reducer and the problem of maintenance effect for earth in aggregate, and anti-chamotte mould polycarboxylate water-reducer of a kind of effective resistance earth disadvantageous effect and preparation method thereof is provided.This anti-chamotte mould water reducer has the performance of good dispersing property and the absorption of anti-earth, and in the situation that aggregate contains mud, its dispersion effect is obviously better than traditional water reducer, and not only water reducer volume reduces, and has improved concrete retention.
For solving the problems of the technologies described above, the technical solution used in the present invention is:
A kind of anti-chamotte mould polycarboxylate water-reducer, it is by unsaturated polyester aklylene glycol ethers monomer a, unsaturated carboxylic acid class monomer b, unsaturated acid hydroxy alkyl ester c, and quaternary ammonium salt cationic unsaturated monomer d obtains by free-radical polymerized under the effect of initiator and chain-transfer agent
Wherein: the mol ratio of described monomer a, monomer b, monomer c, monomer d is 1.0:2.0～4.2:0.2～1.0:0.1～0.5, and monomer a represents with general formula 1:
YO(TO)
m(R
1O)
nH (1)
Wherein Y represents the thiazolinyl of 2～5 carbon atoms; T represents the alkylidene group of 1～3 carbon atom; R
1o represents ethyl oxide or oxidation propyl group; M represent 0 or 1, n represent the molar average adduct number of ethyl oxide or oxidation propyl group, and n is 1～100;
Monomer b represents with general formula 2:
R in formula
2, R
3, R
4be same to each other or different to each other, and represent hydrogen atom separately, methyl or COOM, M represents hydrogen atom or monovalent metal atom;
Monomer c represents with general formula 3:
R in formula
5represent hydrogen atom or methyl, R
6represent ethyl or propyl group;
Monomer d represents with general formula 4:
R in formula
7represent hydrogen atom or methyl, R
8represent amide group or acyloxy, R
9represent ethyl, propyl group or phenyl,
represent the negative ions such as chlorine, bromine, iodine, hydroxide radical, nitrate radical; X is 0 or 1.
Press such scheme, the mol ratio of described monomer b and the total amount of c and monomer a is preferably 3.0～4.4:1.
The present invention also provides the preparation method of above-mentioned anti-chamotte mould polycarboxylate water-reducer:
By various monomer ratio consumptions, by the aqueous solution of unsaturated polyester aklylene glycol ethers monomer a and quaternary ammonium salt cationic unsaturated monomer d in reactor, be warming up to 58～80 ℃, drip the mixed aqueous solution of unsaturated carboxylic acid class monomer b and unsaturated acid hydroxy alkyl ester c, and drip the mixing solutions of initiator and chain-transfer agent simultaneously, in 0.5～3h, drip off, dropwise rear insulation 1～3h, after finishing, reaction is cooled to below 50 ℃, adding alkali, to be neutralized to pH be 6～7, adds water regulation system solid content and obtain anti-chamotte mould polycarboxylate water-reducer.
Press such scheme, the consumption of described chain-transfer agent be monomer b and monomer c quality and 1wt%～5wt%, the consumption of initiator is the 0.1wt%～1.6wt% of monomer a, monomer b, monomer c and monomer d total mass, the time for adding of the mixed aqueous solution of monomer b and monomer c is controlled at 0.5～2.5h, and the time for adding of the mixing solutions of initiator and chain-transfer agent is controlled at 1～3h.
Press such scheme, described unsaturated polyester aklylene glycol ethers monomer a can be allyl polyethenoxy ether, methacrylic Soxylat A 25-7 or 3-methyl 3-butene-1-ol Soxylat A 25-7, and the molecular weight of described monomer a is 1200～2400.Conventional have allyl polyethenoxy ether (molecular weight 1200), methacrylic Soxylat A 25-7 (molecular weight 2400), a 3-methyl 3-butene-1-ol Soxylat A 25-7 (molecular weight 2400).
Press such scheme, described unsaturated carboxylic acid class monomer b can be vinylformic acid, methacrylic acid or toxilic acid etc., is preferably vinylformic acid.
Press such scheme, described unsaturated acid hydroxy alkyl ester c can be Hydroxyethyl acrylate, Propylene glycol monoacrylate, hydroxyethyl methylacrylate or Rocryl 410.
Press such scheme, described quaternary ammonium salt cationic monomer d can be allyl group trimethyl ammonium chloride, (3-acrylamide propyl) trimethyl ammonium chloride or 2-(methacryloyl amido) ethyl-trimethyl salmiac etc.
Press such scheme, described initiator can be persulfate initiator as ammonium persulphate, Potassium Persulphate, Sodium Persulfate, or water-soluble azo initiator is as azo diisobutyl amidine hydrochloride, or redox initiator is as hydrogen peroxide and L-AA, hydrogen peroxide and ferrous sulfate etc., when described initiator is selected redox initiator, before the mixed aqueous solution that adds monomer b and c, add oxidant constituents, then after the mixed aqueous solution that adds monomer b and c, add again reductive agent component.
Press such scheme, described chain-transfer agent is Thiovanic acid, and thiohydracrylic acid or lauryl mercaptan etc., be preferably thiohydracrylic acid.
Press such scheme, described alkali is that mass percent concentration is the NaOH solution of 10wt%-40wt%; Described add water and regulate after system solid content be 40wt%-50wt%.
Anti-chamotte mould polycarboxylate water-reducer of the present invention can mix use also can be used separately with the polycarboxylate water-reducer of other kinds, and while using separately, volume is the 0.1wt%～0.3wt% of gelling material gross weight.
The present invention can be based on monomer a by the anti-chamotte mould polycarboxylate water-reducer of selecting monomer a, monomer b, monomer c, monomer d copolymerization to obtain, b, c, synergy between d reaches the effect of effective inhibition earth disadvantageous effect, wherein unsaturated polyester aklylene glycol ethers monomer a is aggregated on water reducer chain as water reducer provides long side chain, play and provide sterically hindered, disperse the effect of cement, thereby guarantee that water reducer has higher water-reducing rate.Monomer b is aggregated to and on water reducer main chain, plays the effect that the carboxylic group that can adsorb cement granules is provided, thereby has guaranteed that water reducer can better be adsorbed by cement.Monomer c is aggregated to the effect of slowly-releasing adsorption group and the effect of auxiliary shield earth to the absorption of water reducer of providing is provided on water reducer main chain, this is because monomer c is aggregated on water reducer chain as water reducer chain provides carboxylic acid hydroxy alkyl ester group, this group can slowly decompose under cement alkaline environment, discharge carboxylic group and micromolecular alcohol, wherein: thereby carboxylic group can adsorb cement, guaranteed that water reducer is adsorbed on more firmly on cement and is not easy to be adsorbed by earth, thereby the micromolecular alcohol discharging in addition can be intercalation into the absorption of reduction clay to water reducer in clay.Cationic monomer d is aggregated on water reducer chain as water reducer provides the side chain with cation group, thereby acting as of playing suppressed or the activity that reduces earth reduces the absorption of earth to water reducer.Monomer c and monomer d are collaborative to be used, and to suppressing the disadvantageous effect of earth, more produces effect.
Further, the usage ratio between each monomer also can have influence on the performance of monomer effect, and then has influence on the performance of product.Wherein: the too low meeting of consumption of monomer b causes the water-reducing rate of water reducer low, and the too high meeting of consumption makes water reducer function of slump protection bad, thus the consumption of monomer b can not be too low can not be too high, monomer b: monomer a mol ratio is most suitable at 2.0～4.2:1.0.The critical function of monomer c in anti-chamotte mould water reducer, so guarantee the consumption that monomer c is certain, through synthetic study, control monomer c: mol ratio 0.2～1.0:1.0 of monomer a is most suitable, and by the total amount of further control monomer b and c and the mol ratio of monomer a, be 3.0～4.4:1, can guarantee better the performance of this water reducer.This is because the too low meeting of total amount of monomer b and c causes the adsorption group of water reducer few, the absorption of Water-reducing Admixtures To Cements causes water-reducing rate low not, if the total amount of monomer b and c is too high, can reduce the density of side chain in water reducer, this sterically hindered effect that also can reduce water reducer causes water reducer water-reducing rate low.In addition, thereby monomer d gives water reducer cation group suppresses the disadvantageous effect of earth to water reducer, so the consumption of monomer d should not be too low, but the too high meeting of monomer d consumption causes water reducer, water reducer water-reducing rate in the situation that earth content is low is inadequate, so the amount of monomer d is controlled at monomer d: 0.1～0.5:1.0 is most suitable for monomer a mol ratio.The mol ratio of monomer a, monomer b, monomer c, monomer d is controlled as 1.0:2.0～4.2:0.2～1.0:0.1～0.5 in sum, and be 3.0～4.4:1 by the total amount of further control monomer b and c and the mol ratio of monomer a, can guarantee that like this water reducer does not contain high water reducing rate and the high function of slump protection in mud situation at aggregate, also can give water reducer and in the situation that aggregate contains mud, effectively resist the anti-mud performance of earth to water reducer disadvantageous effect.
Beneficial effect of the present invention
(1) in anti-chamotte mould polycarboxylate water-reducer molecular structure of the present invention, contain carboxylic acid hydroxy alkyl ester unit, can reduce the susceptibility of water reducer to earth, carboxylic acid hydroxy alkyl ester can slowly be hydrolyzed and discharge carboxylic group and micromolecular alcohol in cement alkaline environment simultaneously, thereby carboxylic group can adsorb and guaranteed on cement that water reducer is adsorbed on more firmly on cement and is not easy to be adsorbed by earth, thereby the micromolecular alcohol discharging in addition can be intercalation into and in clay, goes to reduce the absorption of clay to water reducer.
(2) in anti-chamotte mould polycarboxylate water-reducer molecular structure of the present invention, there is cationic structural unit simultaneously, can effectively reduce the absorption of earth to polycarboxylate water-reducer, make carboxyl and polyether lateral chain in water reducer molecular structure bring into play respectively absorption cement and the effect that disperses cement, thereby even if ensured diminishing and guarantor's effect of collapsing of water reducer when having clay to exist.
(3) in the situation that aggregate silt content is higher, anti-chamotte mould water reducer with the obvious advantage higher than traditional water reducer.
(4) the present invention reacts simply, adopts single stage method can obtain the finished product by radical polymerization, and product preparation process or the finished product all pollution-free to environment and human body, Product Green environmental protection.
Embodiment
Below in conjunction with embodiment, the present invention is further illustrated, but therefore do not limit the present invention among described scope of embodiments, any change that those of ordinary skills made for the present invention easily realize or change do not deviating under technical solution prerequisite of the present invention, within all will be included into claim scope of the present invention.
Embodiment 1
The allyl group trimethyl ammonium chloride aqueous solution that adds 99.0g water, 240.0g (0.1mol) methacrylic Soxylat A 25-7 (molecular-weight average 2400), 13.6g 50% (0.05mol) in the 1000ml four-hole boiling flask that condenser, thermometer, agitator and constant voltage titration funnel are housed, stirs and is warmed up to 80 ℃.In 2h, drip by 30.2 (0.42mol) vinylformic acid and 2.3g (0.02mol) Hydroxyethyl acrylate are dissolved in to the aqueous solution obtaining in 8.1g water.When dripping vinylformic acid and Hydroxyethyl acrylate monomer solution, with 2.5h, drip by 1.04g thiohydracrylic acid and 4.47g ammonium persulphate are dissolved in to the aqueous solution obtaining in 104.7g water.Thereby after dropwising, be incubated 2h again and complete polyreaction, reaction mixture subsequently, makes pH=6 and adds water that to regulate solid content be 40wt% with the neutralization of 30wt%NaOH solution, obtain anti-chamotte mould polycarboxylate water-reducer HSPC-KN1.
Embodiment 2
2-(methacryloxy) the ethyl-trimethyl salmiac aqueous solution that adds 99.3g water, 240.0g (0.1mol) 3-methyl 3-butene-1-ol Soxylat A 25-7 (molecular-weight average 2400), 12.5g 50% (0.03mol) in the 1000ml four-hole boiling flask that condenser, thermometer, agitator and constant voltage titration funnel are housed, stirring is warmed up to 60 ℃, adds 1.38g 30%H
2o
2solution.In 2.5h, drip by 23.0 (0.32mol) vinylformic acid and 6.5g (0.05mol) Propylene glycol monoacrylate are dissolved in to the aqueous solution obtaining in 7.4g water.When dripping vinylformic acid and Propylene glycol monoacrylate monomer solution, with 3h, drip the aqueous solution by 0.89g thiohydracrylic acid and 0.53gL-dissolution of ascorbic acid are obtained in 27.0g water.Thereby after dropwising, be incubated 1.5h again and complete polyreaction, reaction mixture subsequently, makes pH=6 and adds water that to regulate solid content be 40wt% with the neutralization of 40wt%NaOH solution, obtain anti-chamotte mould polycarboxylate water-reducer HSPC-KN2.
Embodiment 3
(3-acrylamide propyl) the trimethyl ammonium chloride aqueous solution that adds 50.0g water, 120.0g (0.1mol) allyl polyethenoxy ether (molecular-weight average 1200), 4.1g50% (0.01mol) in the 1000ml four-hole boiling flask that condenser, thermometer, agitator and constant voltage titration funnel are housed, stirring is warmed up to 60 ℃, adds 1.64g 30%H
2o
2solution.In 0.5h, drip by 14.4 (0.20mol) vinylformic acid and 13.0g (0.10mol) hydroxyethyl methylacrylate are dissolved in to the aqueous solution obtaining in 6.9g water.When dripping vinylformic acid and hydroxyethyl methylacrylate monomer solution, with 1h, drip the aqueous solution by 1.37g Thiovanic acid and 0.60gL-dissolution of ascorbic acid are obtained in 37.4g water.Thereby after dropwising, be incubated 3h again and complete polyreaction, reaction mixture subsequently, makes pH=7 and adds water that to regulate solid content be 40wt% with the neutralization of 40wt%NaOH solution, obtain anti-chamotte mould polycarboxylate water-reducer HSPC-KN3.
Embodiment 4
(3-acrylamide propyl) the trimethyl ammonium chloride aqueous solution that adds 99.3g water, 240.0g (0.1mol) methacrylic Soxylat A 25-7 (molecular-weight average 2400), 12.4g50% (0.03mol) in the 1000ml four-hole boiling flask that condenser, thermometer, agitator and constant voltage titration funnel are housed, stirs and is warmed up to 58 ℃.In 2.0h, drip by 21.6 (0.30mol) vinylformic acid and 11.5g (0.08mol) Rocryl 410 are dissolved in to the aqueous solution obtaining in 8.3g water.When dripping vinylformic acid and Rocryl 410 monomer solution, with 2.5h, drip by 0.33g thiohydracrylic acid and 0.28g azo diisobutyl amidine hydrochloride are dissolved in to the aqueous solution obtaining in 11.6g water.Thereby after dropwising, be incubated 2h again and complete polyreaction, reaction mixture subsequently, makes pH=6 and adds water that to regulate solid content be 40wt% with the neutralization of 30wt%NaOH solution, obtain anti-chamotte mould polycarboxylate water-reducer HSPC-KN4.
Embodiment 5
2-(methacryloxy) the ethyl-trimethyl salmiac aqueous solution that adds 99.3g water, 240.0g (0.1mol) 3-methyl 3-butene-1-ol Soxylat A 25-7 (molecular-weight average 2400), 12.5g 50% (0.03mol) in the 1000ml four-hole boiling flask that condenser, thermometer, agitator and constant voltage titration funnel are housed, stirs and is warmed up to 58 ℃.In 2.0h, drip by 23.0 (0.32mol) vinylformic acid and 11.6g (0.10mol) Hydroxyethyl acrylate are dissolved in to the aqueous solution obtaining in 8.6g water.When dripping vinylformic acid and Hydroxyethyl acrylate monomer solution, with 2.5h, drip by 1.01g thiohydracrylic acid and 0.48g azo diisobutyl amidine hydrochloride are dissolved in to the aqueous solution obtaining in 28.3g water.Thereby after dropwising, be incubated 2h again and complete polyreaction, reaction mixture subsequently, makes pH=7 and adds water that to regulate solid content be 40wt% with the neutralization of 40wt%NaOH solution, obtain anti-chamotte mould polycarboxylate water-reducer HSPC-KN5.
Comparative example 1
This comparative example provides the both sexes water reducer that does not comprise unsaturated carboxylic acid hydroxy alkyl ester in a kind of polymerization single polymerization monomer.2-(methacryloxy) the ethyl-trimethyl salmiac aqueous solution that adds 99.3g water, 240.0g (0.1mol) 3-methyl 3-butene-1-ol Soxylat A 25-7 (molecular-weight average 2400), 12.5g 50% (0.03mol) in the 1000ml four-hole boiling flask that condenser, thermometer, agitator and constant voltage titration funnel are housed, stirring is warmed up to 60 ℃, adds 1.38g 30%H
2o
2solution.In 2.5h, drip by 23.0 (0.32mol) vinylformic acid is dissolved in to the aqueous solution obtaining in 6.0g water.When dripping acrylic acid solution, with 3h, drip the aqueous solution by 0.69g thiohydracrylic acid and 0.53gL-dissolution of ascorbic acid are obtained in 23.2g water.Thereby after dropwising, be incubated 1.5h again and complete polyreaction, reaction mixture, makes pH=6 with the neutralization of 30%NaOH solution subsequently, obtains this comparative example 1 water reducer, called after BJPC-1.
Comparative example 2
This comparative example provides the water reducer that does not comprise unsaturated carboxylic acid hydroxy alkyl ester and cationic monomer in a kind of polymerization single polymerization monomer.In the 1000ml four-hole boiling flask that condenser, thermometer, agitator and constant voltage titration funnel are housed, add 102.9g water, 240.0g (0.1mol) 3-methyl 3-butene-1-ol Soxylat A 25-7 (molecular-weight average 2400), stirring is warmed up to 60 ℃, adds 1.38g30%H
2o
2solution.In 2.5h, drip by 23.0 (0.32mol) vinylformic acid is dissolved in to the aqueous solution obtaining in 6.0g water.When dripping acrylic acid solution, with 3h, drip the aqueous solution by 0.89g thiohydracrylic acid and 0.53gL-dissolution of ascorbic acid are obtained in 27.0g water.Thereby after dropwising, be incubated 1.5h again and complete polyreaction, reaction mixture, makes pH=6 with the neutralization of 30wt%NaOH solution subsequently, obtains the water reducer of this comparing embodiment 2, called after BJPC-2.
Comparative example 3
The mol ratio that this comparative example provides a kind of polymerization single polymerization monomer a:b:c:d is the water reducer in the scope described in claim not.(3-acrylamide propyl) the trimethyl ammonium chloride aqueous solution that adds 95.7g water, 240.0g (0.1mol) methacrylic Soxylat A 25-7 (molecular-weight average 2400), 24.8g50% (0.06mol) in the 1000ml four-hole boiling flask that condenser, thermometer, agitator and constant voltage titration funnel are housed, stirs and is warmed up to 58 ℃.In 2.0h, drip by 36.0 (0.50mol) vinylformic acid and 11.5g (0.08mol) Rocryl 410 are dissolved in to the aqueous solution obtaining in 11.9g water.When dripping vinylformic acid and Rocryl 410 monomer solution, with 2.5h, drip by 0.71g thiohydracrylic acid and 0.35g azo diisobutyl amidine hydrochloride are dissolved in to the aqueous solution obtaining in 20.1g water.Thereby after dropwising, be incubated 2h again and complete polyreaction, reaction mixture, makes pH=6 with the neutralization of 30wt%NaOH solution subsequently, obtains the water reducer of this comparative example 3, called after BJPC-3.
Comparative example 4
The mol ratio that this comparative example provides a kind of polymerization single polymerization monomer a:b:c:d is the water reducer in the scope described in claim not.(3-acrylamide propyl) the trimethyl ammonium chloride aqueous solution that adds 99.3g water, 240.0g (0.1mol) 3-methyl 3-butene-1-ol Soxylat A 25-7 (molecular-weight average 2400), 12.4g50% (0.03mol) in the 1000ml four-hole boiling flask that condenser, thermometer, agitator and constant voltage titration funnel are housed, stirs and is warmed up to 58 ℃.In 2.5h, drip by 27.4 (0.38mol) vinylformic acid and 1.16g (0.01mol) Hydroxyethyl acrylate are dissolved in to the aqueous solution obtaining in 7.14g water.When dripping vinylformic acid and Hydroxyethyl acrylate monomer solution, with 3h, drip by 0.78g thiohydracrylic acid and 0.51g azo diisobutyl amidine hydrochloride are dissolved in to the aqueous solution obtaining in 24.5g water.Thereby after dropwising, be incubated 1.5h again and complete polyreaction, reaction mixture, makes pH=6 with the neutralization of 40wt%NaOH solution subsequently, obtains the water reducer of this comparative example 4, called after BJPC-4.
Implementation result
The clean slurry test of implementation result experiment is carried out according to GB GB/T 8077-2012 < < concrete admixture uniformity test method > >, and polynite replaces the cement of respective quality according to inner blending method.Mortar test is carried out with reference to GB GB/T 19671-1999 < < Test method for strength of hydraulic cement mortar > > step, cement 550g, sand 1350g, water 220g, mixes in water reducer.Testing concrete performance carries out with reference to GB GB/T 50080-2002 < < Standard for test methods of properties of ordinary concrete mixture > >.The volume of water reducer is the solid volume of folding.
1, only starch degree of mobilization experiment
Clean slurry experiment cement is reference cement and two kinds of cement of Hua Xin cement PO42.5.Experimental result is in Table 1:
Table 1, mix the clean slurry experiment of polynite
2, Mortar'S Flowability experiment
The new cement 550g of China, standard sand 1350g, water 220g, mixes in water reducer, and polynite replaces the sand of respective amount.Experimental result is as following table 2:
Table 2, additional polynite water reducer Mortar'S Flowability experiment
3 concrete experiments
(1) containing the test of mud river sand concrete
Concrete mix is as following table 3:
Table 3 concrete mix
Test result is as following table 4:
Table 4 concrete test result
More than experiment shows that aggregate contains in the situation of mud, and anti-its dispersion effect of chamotte mould polycarboxylate water-reducer HSPC-KN is obviously better than traditional water reducer, and not only volume is low, and retention is better.
Claims (10)
1. an anti-chamotte mould polycarboxylate water-reducer, it is characterized in that: it is by unsaturated polyester aklylene glycol ethers monomer a, unsaturated carboxylic acid class monomer b, unsaturated acid hydroxy alkyl ester c, and quaternary ammonium salt cationic unsaturated monomer d obtains by free-radical polymerized under the effect of initiator and chain-transfer agent
Wherein: the mol ratio of described monomer a, monomer b, monomer c, monomer d is 1.0:2.0～4.2:0.2～1.0:0.1～0.5, and monomer a represents with general formula 1:
YO(TO)
m(R
1O)
nH (1)
Wherein Y represents the thiazolinyl of 2～5 carbon atoms; T represents the alkylidene group of 1～3 carbon atom; R
1o represents ethyl oxide or oxidation propyl group; M represent 0 or 1, n represent the molar average adduct number of ethyl oxide or oxidation propyl group, and n is 1～100;
Monomer b represents with general formula 2:
R in formula
2, R
3, R
4be same to each other or different to each other, and represent hydrogen atom separately, methyl or COOM, M represents hydrogen atom or monovalent metal atom;
Monomer c represents with general formula 3:
R in formula
5represent hydrogen atom or methyl, R
6represent ethyl or propyl group;
Monomer d represents with general formula 4:
R in formula
7represent hydrogen atom or methyl, R
8represent amide group or acyloxy, R
9represent ethyl, propyl group or phenyl,
represent chlorine, bromine, iodine, hydroxide radical, nitrate radical negative ion; X is 0 or 1.
2. anti-chamotte mould polycarboxylate water-reducer according to claim 1, is characterized in that: the mol ratio of described monomer b and the total amount of c and monomer a is 3.0～4.4:1.
3. the preparation method of anti-chamotte mould polycarboxylate water-reducer claimed in claim 1, it is characterized in that: by various monomer ratio consumptions, by the aqueous solution of unsaturated polyester aklylene glycol ethers monomer a and quaternary ammonium salt cationic unsaturated monomer d in reactor, be warming up to 58～80 ℃, drip the mixed aqueous solution of unsaturated carboxylic acid class monomer b and unsaturated acid hydroxy alkyl ester c, and drip the mixing solutions of initiator and chain-transfer agent simultaneously, in 0.5～3h, drip off, dropwise rear insulation 1～3h, after finishing, reaction is cooled to below 50 ℃, adding alkali, to be neutralized to pH be 6～7, add water regulation system solid content and obtain anti-chamotte mould polycarboxylate water-reducer.
4. the preparation method of anti-chamotte mould polycarboxylate water-reducer according to claim 3, it is characterized in that: the consumption of described chain-transfer agent be monomer b and monomer c quality and 1wt%～5wt%, the consumption of initiator is the 0.1wt%～1.6wt% of monomer a, monomer b, monomer c and monomer d total mass, the time for adding of the mixed aqueous solution of monomer b and monomer c is controlled at 0.5～2.5h, and the time for adding of the mixing solutions of initiator and chain-transfer agent is controlled at 1～3h.
5. the preparation method of anti-chamotte mould polycarboxylate water-reducer according to claim 3, it is characterized in that: described unsaturated polyester aklylene glycol ethers monomer a can be allyl polyethenoxy ether, methacrylic Soxylat A 25-7 or 3-methyl 3-butene-1-ol Soxylat A 25-7, and the molecular weight of described monomer a is 1200～2400.
6. the preparation method of anti-chamotte mould polycarboxylate water-reducer according to claim 3, is characterized in that: described unsaturated carboxylic acid class monomer b can be vinylformic acid, methacrylic acid or toxilic acid.
7. the preparation method of anti-chamotte mould polycarboxylate water-reducer according to claim 3, is characterized in that: described unsaturated acid hydroxy alkyl ester c can be Hydroxyethyl acrylate, Propylene glycol monoacrylate, hydroxyethyl methylacrylate or Rocryl 410.
8. the preparation method of anti-chamotte mould polycarboxylate water-reducer according to claim 3, is characterized in that: described quaternary ammonium salt cationic monomer d can be allyl group trimethyl ammonium chloride, (3-acrylamide propyl) trimethyl ammonium chloride or 2-(methacryloyl amido) ethyl-trimethyl salmiac.
9. the preparation method of anti-chamotte mould polycarboxylate water-reducer according to claim 3, it is characterized in that: described initiator can be persulfate initiator or water-soluble azo initiator or redox initiator, when described initiator is selected redox initiator, before the mixed aqueous solution that adds monomer b and c, add oxidant constituents, then after the mixed aqueous solution that adds monomer b and c, add again reductive agent component; Described chain-transfer agent is Thiovanic acid, thiohydracrylic acid or lauryl mercaptan.
10. the preparation method of anti-chamotte mould polycarboxylate water-reducer according to claim 3, is characterized in that: described alkali is that mass percent concentration is the NaOH solution of 10wt%-40wt%; Described add water and regulate after system solid content be 40wt%-50wt%.
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